Insecticidal compositions



United States Patent 2,830,928 INSECTICIDAL COMPOSITIONS Robert J. Harker, Terre Haute, Ind., assignor to Commercial Solvents Corporation, Terre Haute, Ind., 21 corpo- 2 ture of 2-nitro-1,l-bis-(p-chlorophenyl) propane and 2- nitrO-l,l-bis-(p-chlorophenyDbutane, and a mixture of 2- nitro l,l-bis-(p-chlorophenyl)butane, 2-nitro-1,1-bis-(pchloropheny1)propane and 1,1,1-trichloro-2,2-bis-(p-chloration of Maryland 5 rophenyDethane. As oils suitable for use in my com- No Drawing A fi afi A yfl 27, 1954 position I can use any of the non-drying or semi-drying Serial No. 426,640 vegetable Oils, such as cottonseed oil, peanut oil, soybean Claims L 167 30) v oil, corn oil, castor oil, sesame oil and palm oil. Solvents My invention relates to insecticidal compositions. Suitable use 111 my i i l compssifions inclufle More particularly, it relates to residual deposits of such 10 F rg Sch/em Whlch W111 dlssclve both the acme compositions with enhanced immediate activity insecticide and the oil added, such as benzene, Xylene,

Insecticides as a group often vary widely in Physical kerosene, petroleum naphthas, and light hydrocarbons in characteristics. Most insecticides are crystalline comgtmel'alpounds However, some of the more recently developed The active insectlcidal ingredient may be included in insecticides take the form of viscous oils in the technithe P P Q m any de S11'ed concen-tmnon so long as cal grades. These are generally marketed to the insecf Orgamc Selvent P to finder the ageflt ticide trade as mobile solutions in organic solvents, and mgblle- The Vegetable mgredlgnt can be added In sometimes with added emulsifiers to render them suitable Haunts 9 3 j f to about 60% of the Weight for mixing withtwaten For use, these insecticides are 0 of the active insectlcidal ingredient. I prefer to include a generally mixed with powdered inert ingredients to form Vegetable 9 In all amfmnt g ng from about to powders for dusting, are dissolved in additional organic fl 40% of the Y of the msectlclfiial solvents for spraying, or, with added emulsifiers, are I S An Organ: sohent F be mchfded any sprayed as emulsions in oesired amount so long as su;c1 ent solvent is present to Among the recently developed insecticides the techninFake the 9 mgredlents Lhave found 1t f cal grades of which occur as Viscous oils are sirable to include the organic solvent in a concentration bis (p chlorophenyl)propane and of at least about 20% of the total composition. rophenyl)butane, and mixtures of these two insecticides The followmg F Serve ,to,lnustrate mven' which are produced in the manner set forth in United but I do mt to be cd to the disclosed States Patent 2,516,186, issued to H. B. Hass and R. T. compourfds a scope of my mventwfl 18 as Blickenstafi on July 25 1950 defined in this specification and appended claims.

It has now been found that these particular insec EXAMPLE I ticides, when dissolved in organic solvents and sprayed Li id concentrates of a mixture of 2 parts of 2. m on surfaces to afford protection from insects, are not im- 1,1-bis (p-ch1cropheny1)butane and l-part of .Z-nitromediately effective as insecticides, but have to undergo 1,l-bis-(p-chlorophenyl)propane were prepared i a period of conditioning before reaching their full efiecing 25% of the mixed insecticides, 10% of a non-drying tiveness. or semi-drying vegetable oil in some of the samples, and I have now discovered an insecticidal composition of the remainder an organic solvent. For spraying there enhanced immediate activity which comprises an insecwas added to these concentrates 2% by weight of a standticide selected from the group consisting of 2-nitro1,l- 40 a d commercial emulsifier (Triton X-155), and they bis (p chlorophenyl)propane, 2-nitro-l,l-bis-(p-chlorowere then diluted with 4 volumes of water and sprayed on pheny1)butane, mixtures of 2-nitro-1,1-bis-(p-chloroplywood panels. The spray was adjusted to deposit 200 phenyl)propane and 2-nitro-l,l-bis-(p-chlorophenyl)bumilligrams of the active insecticide per square foot of tane, and mixtures of 2-nitro-1,l-bis-(p-chlorophenyl) the panel. Three days after spraying groups of 100 adult P p -(P- p ny n and female houseflies of an insecticide-resistant strain, M. 1,1,1-trichloro-2,2-bis-(p-chlorophenyl)ethane and a vegdomestic, Roberds resistant strain, were exposed to the etable oil selected from the group consisting of non-dryplywood panels containing the residual deposits. The ing and semi-drying oils in a mutual organic solvent. flies were retained under petri dishes 4 inches in diameter This composition has been found not to be subject to the for periods of 30 minutes in contact with the plywood objection of previous compositions in that it does not re panels. At the end of the 30 minute exposure period the quire any period of conditioning after it is deposited, but flies were transferred to clean wire cages and the percent is immediately effective to its fullest extent as an insecmortalities determined at the end of 24 hours. This proticide. cedure was repeated with new groups of the same strain My compositions consist of the oily, viscous, insecof hcuseflies after the residual deposits had aged for the ticides, or mixtures thereof and a very slow-drying vegperiods indicated, i. e., one, two, three, four, and seven etable oil in a mutual organic solvent. As the active weeks. The results of exposures of each group of flies to ingredient of my new compositions I can use any of the the diflerent test deposits of increasing age are set out following insecticides: 2-11itro-1,l-bis-(p-chlorophenyl)- in Table I below as percent mortalities 24 hours after propane, Z-nitro-l,1-bis-(p-chlorophenyl)butane, a mixeach exposure.

Tablel Insecticide Additive 24 hour mortality (percent) Solvent Type Dosage 011 Dosage, 3 1 2 3 4 7 rug/ft. mg./ft. days wk wks. wlrs. wks. wks.

A 200 Xylene 0 O 0 0 42 A.. 200 LHO 42 0 4 5 s 25 200 LHOL- 47 22 39 as 40 200 LHOL. 93 69 3s 22 59 31 20o LHC 73 54 51 25 s3 98 A is a mixture of 1 part 2-nitro-1,1-bis-(pchlorophenyhpropane and 2 parts 2-nitro- 1,1-bis-(p'chlorophonynbutanc.

- C. S. O. is cottonseed oil; P. O. is peanut oil; S. O. is soybean oil.

I LHO is a light hydrocarbon solvent (Sovaclde 544-G of Socony-Vacuum 011 Company).

3 EXAMPLE 11 The liquid concentrate of a mixture of 1 part of a 1:2 mixture of 2-nitro-1,l-bis-(p-chlorophenyl)propane and 2-nitro-1,l-bis-(p-chlorophenyl)butane and 1 part of 1,1,1-trichloro-2,2-bis-(p-chlorophenyl)ethane was prepared containing 50% of the mixed insecticide, of a non-drying or semi-drying vegetable oil in some of the samples, and the remainder an organic solvent. For spraying there was added to this concentrate 2% by weight of a standard commercial emulsifier (Triton X-155), and they were then diluted with 4 volumes of water and sprayed on plywood panels. The spray was adjusted to deposit 400 mg. of the active insecticides per square foot of the panel. Groups of one hundred adult female houseflies of M. domestica, Roberds resistant strain, were exposed in the same manner as set out in Example I above to these residual deposits for a minute period. The results of exposures to the different residual deposits at the indicated ages of the deposits are set out in Table II below as percent mortality in each group of 100 flies 24 hours after exposure.

4 Table III FLY POPULATIONS PER SQUARE YARD 2 Barn B treated with 25% 2-nitro-1,l-bis-(p-chlorophenyl) propane and butane and 25% 1,1,1-trichloro-2,2-bis(p-chlorophenyDethane emulsion.

1 B is a mixture of 1 part of a 1 to 2 mixture of 2nitro-1,1-bis-(p-chlorophenyl propane and 2-nitro-l,l-bis-(p-chlorophenyl)butane and 1 part 1,1,1-trichloro-2,2-bisp-chlorophenyDethane.

1 C. S. O. is cottonseed oil; P. 0. is peanut oil; S. O. is soybean oil.

i LHO is a light hydrocarbon solvent, Sovacide 544-6, a commercial product of Socony- Vacuum Oil Company.

EXAMPLE 111 Field tests of my new insecticidal compositions were conducted which confirmed their eflectiveness against the strains of flies normally occurring in and about dairy barns, areas of high fly infestations. These field tests were conducted in three operating dairy barns, including one in a location favoring a high potential rate of reinfestation, one favoring a low potential rate of re-infestation, and one in a location having a medium potential rate of re-infestation. The dairy barn in the medium potential rate location was untreated and thus served to indicate normal fly populations. The dairy barn in the low potential rate location was sprayed at the rate 200 mg. of insecticide per square foot of surface area with an emulsion of the following percentage composition in 3 volumes of water: 25% a 1:2 mixture of 2-nitr0-l,1- bis-(p-chlorophenyl)propane and 2-nitro-l,l-bis-(p-chlorophenyl)butane, 10% cottonseed oil, 2% commercial emulsifier, and 63% xylene. The high potential rate dairy barn was sprayed at the rate of 400 mg. of all insecticides per square foot of surface area with an emulsion of the following percentage composition in 3 volumes of water: 25% a 1:2 mixture of 2-nitro-1,1-bis- (p-chiorophenyDpropane and 2-nitro-1,l-bis-(p-chlorophenyl)butane, 25% 1,1,1-trichloro-2,2-bis-(p-chlorophenyDethane, 10% cottonseed oil, 2% commercial emulsifier, and 38% xylene. Fly populations per square yard were determined at the indicated intervals after spraying both inside and outside immediately adjacent to the three dairy barns. The results recorded in Table III below are the average of the four highest counts taken out of samples on each recorded reading.

My new insecticidal compositions can be utilized as sprays after dilution. They may be further diluted with additional organic solvents to the desired concentration for spraying on any inert surface. They can also be di luted with Water after the inclusion of any suitable emulsifiers to disperse the organic solvent in the water. This latter is the preferred method of application of my new composition to growing plants.

Now having described my invention what I claim is:

1. An insecticidal composition of enhanced immediate activity which comprises an insecticide selected from the group consisting of 2-nitro-1,l-bis-(p-chlorophenyl)propane, Z-nitro-l,l-bis-(p-chlorophenyl)butane, mixtures of 2-nitro-1,l-bis-(p-chlorophenyl)propane and 2-nitro-1,1- bis-(p-chlorophenyl)butane, and mixtures of 2-nitro-l,lbis- (p-chlorophenyl propane, 2-nitrol 1 -bis-(-p-chlorophenyl)butane, and 1,1,1-trichloro-2,2-bis-(p-chlorophenyl)ethane and from about 5 to 60% by weight, based on the weight of the activeinsecticidal component, of a slow-drying vegetable oil selected from the group consisting of non-drying and semi-drying oils in a mutual organic solvent.

2. An insecticidal composition of enhanced immediate activity which comprises a mixture of 2-nitro-l.1-bis-(pchlorophenyl propane and Z-nitro- 1 l-bis- (p-chlorophenyl)butane and a slow-drying vegetable oil selected from the group consisting of non-drying and semi-drying oils in a mutual organic solvent.

3. The composition of claim 2 wherein the vegetable oil is peanut oil.

4. The composition of claim 2 wherein the vegetable oil is soybean oil.

5. An insecticidal composition of enhanced immediate activity which comprises a mixture of 2-nitro-1,1-bis-(pchlorophenyl) propane, 2nitro-1,l-bis-(p-chlorophenyl) butane and 1,l,1-trichl'oro-2,2-bis-(p-chlorophenyl)ethane and from about 5 to 60% by weight, based on the weight of the active insecticidal component, of a slow-drying vegetable oil selected from the group consisting of nondrying and semi-drying oils in a mutual organic solvent.

6. The composition of claim 5 wherein the vegetable oil is cottonseed oil.

7. The composition of claim 5 wherein the vegetable oil is soybean oil.

8. The composition of claim 5 wherein the vegetable oil is peanut oil.

9. In the manufacture of spraying insecticides wherein a mobile liquid insecticidal solution is produced by dissolving in an organic solvent an insecticide selected from the group consisting of 2-nitro-1,l-bis-(p-chlorophenyl)- propane, 2-nitro-l,l-bis-(p-chlorophenyDbutane, mixtures of Z-nitro-l,l-bis-(p-chlorophenyl)propane and 2- nitro-1,1bis-(p-chlorophenyl)butane, and mixtures of 2-nitro-1,1-bis-(p-chlorophenyl)propane, 2-nitro-l,1-bis- (p-chlorophenyl)butane and 1,1,l-trichloro-2,2-bis-(pchlorophenyDethane; the improvement which comprises incorporating in such a liquid solution from about 5 to 60% by weight, based on the weight of the active insecticidal component, of a slow-drying vegetable oil which is soluble in said organic solvent, whereby said insecticidal solutions reach their full insecticidal effectiveness immediately they are applied to a surface without requiring a preliminary period of conditioning.

10. In the protection of buildings from insects, the process which comprises applying to the walls of a building a coating of a liquid insecticide comprising an active insecticidal component selected from the group consisting of 2-nitro-1,1-bis-(p-chlerophenyDpropane, 2-nitro- 1,l-bis-(p-chlorophenyl)butane, mixtures of 2-nitro-1,1- bis-(p-chlorophenyl)propane and 2-nitro-1,1-bis-(p-chlorophenyl)butane, and mixtures of 2-nitro-1,l-bis-(pchlorophenyl)propane, Z-nitro-l,1-bis-(p-chlor0phenyl) butane and 1,l,1-trichloro-2,2-bis-(p-chlorophenyl)ethane; said liquid insecticide having incorporated therein from about 5 to by weight, based on the weight of the active insecticidal component, of a slow-drying vegetable oil and a mutual solvent for the active insecticidal component and the vegetable oil, whereby the insecticide achieves its full insecticidal effectiveness immediately without requiring a preliminary period of conditioning.

References Cited in the file of this patent OTHER REFERENCES Ind. and Eng. Chem., December 1951, vol. 43, No. 12, pp. 2875-2878.

Soap and Sanitary Chemical, March 1947, p. 141.

Brown: Insect Control by Chemicals, 1951, p. 195. 

1. AN INSECTICIDAL COMPOSITION OF ENHANCED IMMEDIATE ACTIVITY WHICH COMPRISES AN INSECTICIDE SELECTED FROM THE GROUP CONSISTING OF 2-NITRO-1,1-BIS (P-CHLOROPHENYL)PROPANE, 2-NITRO-1,1-BIS (P-CHLOROPHENYL)BUTANE, MIXTURES OF 2-NITRO-1,1-BIS(P-CHLOPHENYL)PROPANE AND 2-NITRO-1,1BIS-(P-CHLORPHNEYL)BUTANE, AND MIXTURES OF 2-NITRO-1,1BIS-(P-CHLOROPHENYL)PROPANE, 2-NITRO-1,1-BIS(P-CHLOROPHENYL)BUTANE, AND 1,1,1-TRICHLORO-2,2-BIS-(P-CHLOROPHENYL)ETHANE AND FROM ABOUT 5 TO 60% BY WEIGHT, BASED ON THE WEIGHT OF THE ACTIVE INSECTICIDAL COMPONENT, OF A SLOW-DRYING VEGETABLE OIL SELECTED FROM THE GROUP CONSISTING OF NON-DRYING AND SEMI-DRYING OILS IN A MUTUAL ORGANIC SOLVENT. 